THE BRITISH COAL-TAR INDUSTRY THE BRITISH COAL-TAR INDUSTRY ITS ORIGIN, DEVELOPMENT, AND DECLINE EDITED BY WALTER M. GARDNER, M.Sc., F.I.C. PRINCIPAL OF THE BRADFORD TECHNICAL COLLEGE ; EDITOR OF THE "JOURNAL OF THE SOCIETY OF DYERS AND COLOURISTS" WITH ILLUSTRATIONS PHILADELPHIA J. B. LIPPINCOTT COMPANY LONDON : WILLIAMS & NORGATE V CONTENTS INTRODUCTION .... vii I. 1868. THE ANILINE OR COAL-TAR COLOURS. By W. H. PERKIN, F.R.S. (Cantor Lectures) . . i II. 1870. THE ARTIFICIAL PRODUCTION OF ALIZARINE. By Professor H. E. ROSCOE, F.R.S. . 46 III. 1879. THE HISTORY OF ALIZARIN AND ALLIED COLOURING MATTERS. By W. H. PERKIN, F.R.S. ... 54 IV. 1880. THE NEWER ARTIFICIAL COLOURING MATTERS DERIVED FROM BENZENE. By R. J. FRISWELL, F.C.S., F.I.C. ... . 60 V. 1881. INDIGO AND ITS ARTIFICIAL PRODUCTION. By Pro- fessor H. E. ROSCOE, LL.D., F.R.S. . . .71 VI. 1885. THE COLOURING MATTERS PRODUCED FROM COAL- TAR. By W. H. PERKIN, F.R.S 75 VII. 1886. RECENT PROGRESS IN THE COAL-TAR INDUSTRY. By Professor Sir H. E. ROSCOE, M.P., LL.D., F.R.S. 106 VIII. 1886. THE SCIENTIFIC DEVELOPMENT OF THE COAL-TAR COLOUR INDUSTRY. By Professor R. MELDOLA, F.C.S., F.I.C. . . .121 IX. 1896. THE ORIGIN OF THE COAL-TAR COLOUR INDUSTRY AND THE CONTRIBUTION OF HOFMANN AND HIS PUPILS. (Hofmann Memorial Lecture.) By W. H. PERKIN, Ph.D., D.C.L., F.R.S. , . . 141 X. 1901. THE SYNTHESIS OF INDIGO. By Professor R. MELDOLA, F.R.S., F.I.C. . . 188 XI. 1901. THE RELATIVE PROGRESS OF THE COAL-TAR IN- DUSTRY IN ENGLAND AND GERMANY DURING THE PAST FIFTEEN YEARS. By ARTHUR G. GREEN, F.I.C., F.CS. . 189 XII. 1901. THE INDIGO CRISIS 204 XIII. 1902. APPLIED CHEMISTRY, ENGLISH AND FOREIGN. By Sir J. DEWAR, M.A., LL.D., D.Sc., F.R.S. . .222 XIV. 1903. THE RELATION BETWEEN SCIENTIFIC RESEARCH AND CHEMICAL INDUSTRY. By Professor R. MELDOLA, F.R.S 227 349277 vi THE BRITISH COAL-TAR INDUSTRY PAGE XV. 1905. HISTORY OF THE COAL-TAR COLOUR INDUSTRY BETWEEN 1870 AND 1885. By Professor R. MELDOLA, F.R.S. ... . .228 XVI. 1906. NOTE ON THE PERKIN JUBILEE . . 232 XVII. 1908. PERKIN OBITUARY NOTICE. By Professor R. MELDOLA, F.R.S. . ... 233 XVIII. 1908. THE FOUNDING OF THE COAL-TAR COLOUR INDUSTRY. By Professor R. MELDOLA, F.R.S. . . 234 XIX. 1908. LETTER FROM PROFESSOR H. CARO TO PROFESSOR R. MELDOLA, MAY 1908 . . . -257 XX. 1910. TINCTORIAL CHEMISTRY, ANCIENT AND MODERN. By Professor R. MELDOLA, F.R.S. . . . 259 XXI. 1910. PATENT LAW IN RELATION TO THE DYEING INDUSTRY. By A. G. BLOXAM, F.I.C. . . 269 XXII. 1910. THE COAL-TAR COLOUR INDUSTRY OF ENGLAND: CAUSES OF ITS PROGRESS AND RETARDATION. By I. SINGER 280 XXIII, 1914. THE ARTIFICIAL COLOUR INDUSTRY AND ITS POSI- TION IN THIS COUNTRY. By F. M. PERKIN, Ph.D., F.I.C. . . 298 XXIV. 1914. THE SUPPLY OF CHEMICALS TO BRITAIN AND HER DEPENDENCIES. By Sir WILLIAM A. TILDEN, D.Sc., LL.D., F.R.S. . . 315 XXV. 1914. BRITAIN AND GERMANY IN RELATION TO THE CHEMICAL TRADE. By WILLIAM R. ORMANDY, D.Sc., F.C.A. . 335 XXVI. 1914. THE MANUFACTURE OF ANILINE DYES IN ENGLAND. By The Right Hon. Lord-Justice MOULTON, P.C., K.C., F.R.S. . .351 XXVII. 1915. GERMAN CHEMICAL INDUSTRY THIRTY YEARS AGO. By The Right Hon. Sir H. ROSCOE, F.R.S. . 365 XXVIII. 1915. THE MANUFACTURE OF DYESTUFFS IN BRITAIN. By Professor W. M. GARDNER, M.Sc., F.I.C. . . 371 XXIX. 1915. THE CHEMICAL INDUSTRIES OF GERMANY. By Professor P. FRANKLAND, F.R.S. . . -379 XXX. 1915. PATENT LAW REFORM. By J. W. GORDON, K.C. . 389 XXXI. 1915. THE SUPPLY OF DYEWARES. By Professor R. MELDOLA, D.Sc., LL.D., F.R.S. .... 401 XXXII. 1915. THE POSITION OF THE ORGANIC CHEMICAL IN- DUSTRY. By Professor W. H. PERKIN, F.R.S. . 407 INDEX OF NAMES 429 INDEX OF COLOURING MATTERS 434 TABULAR AND STATISTICAL INFORMATION . ... 437 INTRODUCTION As a side issue of the war the industry of the manufacture of synthetic dyestuffs has been brought prominently before the public during the past twelve months. And this has occurred not because of its magnitude for the annual value of the products used in Britain did not much exceed 2,000,000, but because the products were essential to the carrying on of the great textile industries of the country, and they were chiefly imported from Germany. It was quickly recognised that our virtual dependence upon Germany for dyestuffs jeopardised our textile trade and many others, such as the manufacture of paints, which involve the use of pigments ; and the annual value of the industries concerned cannot be less than 220,000,000. The stock of dyewares held in this country is never equal to more than a few months* supply, and the processes involved in their production are of such a nature that the manufacture cannot quickly be improvised. Realising therefore that the resources of private enterprise were unequal to the task of making the necessary provision, the Government appointed a commission of inquiry which eventually resulted in the formation of a State-aided limited company British Dyes Ltd. established to manufacture or otherwise provide synthetic dyestuffs on a scale commensurate with the national requirements. The history of the origin and development of the coal-tar colour industry is of great interest not only to the chemist and the student of industrial economics, but also to the politician, the leader of industry, and even to the general reader. To each of vii viii THE BRITISH COAL-TAR INDUSTRY these it has a significant message. The industry which originated and received its early development in this country has grown to be one of great profit and importance, but after a period of much prosperity here (1856 to about 1870) it became gradually more and more centralised in Germany, and has latterly been one of her most profitable industries ; the average dividend paid by the six largest manufacturing firms being upwards of 20 per cent, on a nominal capital of about 8,000,000, which represents only a small fraction of the capital actually expended, most of which has been written off out of profits. The development in Germany of many other associated industries has been the direct outcome of the success of their dyestuffs industry ; for example, the production of synthetic medicines, scents and flavourings, the manufacture of photo- graphic drugs and of fine chemicals generally, the production of artificial fertilisers and of high explosives, and the incidental production of the necessary reagents such as sulphuric acid and caustic soda on an enormous scale. The ramifications of the influence of the coal-tar colour industry in Germany are indeed most astonishing, and a close investigation of the causes of their success will well repay those who are responsible for the future success of British industry. It is with the object of affording easily accessible material for such an inquiry that this book has been compiled. It comprises the chief lectures and addresses given in this country on the subject since the establishment of the industry by Perkin in 1856 to the present day. The papers are given in chronological order, and the book naturally divides itself into two portions, the first twenty-two papers (pp. i to 297) dealing with the history and development of the industry, and the latter portion (Papers XXIII. to XXXIL, pp. 298 to 427) dealing with the problem as it has presented itself since the outbreak of the war. The reasons given for the relative decline of the British industry and its phenomenal development in Germany are numerous and varied. Amongst the former may be mentioned INTRODUCTION ix the supposed lack of well-trained chemists in this country, our admitted early neglect of chemical research, defects in our patent laws, the excise restrictions on alcohol, our fiscal system, want of enterprise and of co-operation amongst the British manufacturers, apathy of successive Governments towards industry (as distinct from commerce), and the early neglect of science by the old uni- versities which is not unconnected with a corresponding ignorance and neglect on the part of our legislators and the general mass of citizens. These various topics are all dealt with in one or other of the papers reprinted herein, and they have a direct bearing not only on industries based on organic chemistry such as those men- tioned in a previous paragraph, but have also a profound bear- ing on the general question of the relation of science to industry. And it cannot be too often or too strongly stated that the future of British industry depends on a full utilisation of science in our industries. One point which is frequently lost sight of in discussing the reasons for our virtual loss of the coal-tar colour industry is that this industry has not been largely developed in any country other than Germany. If countries differing so widely in fiscal, excise, and patent laws, governmental and public appreciation of science, industrial conditions, etc., as Britain, France, and the United States, are equally unable to develop a particular industry which flourishes in Germany, this appears to point to the existence of some specially favourable set of conditions in Germany rather than to the action of some deterrent condition in Britain. The compiler of the book desires to express his great in- debtedness to the authors of the various papers, and to the editors of the journals in which they originally appeared, for their kind permission to reproduce them herein. WALTER M. GARDNER. BRADFORD, September ist, 1915. L: 1868 THE ANILINE OR COAL-TAR COLOURS BY W. H. PERKIN, F.R.S. (Cantor Lectures : Journal of the Society of Arts, 1868, pp. 99, 109, 121) I COAL TAR, BENZOL, NITROBENZOL, ANILINE, AND ANILINE PURPLE OR MAUVE IN this short course of lectures it is my desire to bring before you a somewhat condensed history of the artificial colouring matters, generally known as the " coal-tar colours." By this designation it is not meant to imply that colouring matters actually exist in coal tar, and may, therefore, be extracted from it, but that coal tar is the source of certain products which, when changed by various chemical processes, are capable of yielding coloured derivatives. You will thus perceive that it is important for us to consider the various means employed to obtain the raw materials before giving our attention to the colouring matters themselves. We will, therefore, at once proceed to the considera- tion of "coal tar," its formation and constitution. Coal tar consists of the oily fluid formed by the destructive distillation of coal, and is obtained as a secondary product in the manufacture of coal gas. Originally, coal tar was a great nuisance to the gas manufacturer, and it was often a problem to him what he should do with it. I need scarcely say that this state of things is now changed. In the gasworks the coal is distilled in large retorts, sometimes twenty-five or thirty feet in length. They are made of fireclay or iron, and several are arranged in one furnace, or oven, as it is usually termed. Each retort is fitted with an iron mouthpiece, from which a vertical tube rises, the mouth- piece also having a door fastened with a cross-bar and screw. i 2 THE BRITISH COAL-TAR INDUSTRY When in use these retorts are rapidly filled with coal by means of a proper scoop, and then the doors luted and fixed so as to be airtight. Distillation commences immediately, as the retorts are constantly kept red-hot. The gas and other products which form pass up the front vertical pipe (connected with the mouthpiece), through a bend, and down into a long horizontal tube, called the " hydraulic main/' Here most of the oily pro- ducts condense, and as they accumulate pass on with the gas down the general main and flow into a tank provided for their reception. These oily products constitute " coal tar." The coal gas, leaving this tar behind, passes on to the condensers, and deposits a second but smaller quantity of tar, and is then purified and stored in the gas holders. The gas, however, does not interest us now. I am here distilling some coal in a small glass retort, the beak of which is inserted into one of the openings of a three-necked receiver. The second opening is connected with a tube, so that the gaseous products may be examined, whilst the third and lower one is fitted to a small bottle, in which you see we have already obtained a quantity of an oily fluid. This is our coal tar. Having now seen how coal tar is produced, we will consider of what it consists. Coal tar is by no means a definite body, but contains a great number of different substances, as a glance at the following table will show : TABLE I. PRODUCTS OF THE DISTILLATION OF COAL. Name. Formula. Boiling-point Centigr. Hydrogen .... HH Marsh gas (hydride of methyl) (CH 3 )H ... Hydride of hexyl . (C 6 H 13 )H 65 Hydride of octyl . (C 8 H 17 )H 106 Hydride of decyl . (CioH 21 )H 'S3 Olefiant gas (ethylene) . C 2 H 4 Propylene (tritylene) C 8 H 6 ... Caproylene (hexylene) . C 6 H 12 55 (Enanthylene (heptylene) C 7 H 14 99 Paraffin cjau Acetylene C 2 H 2 ... Benzol C 6 H 6 80-8 Parabenzol C 6 H 6 97'5 Toluol . C 7 H 8 no Xylol . C 8 H 10 139 THE ANILINE OR COAL-TAR COLOURS TABLE I. continued. Name. Formula. Boiling-point Centigr. Cumol ...... C 9 H 12 148-4 Cymol ...... C 10 H 14 1707 Naphthaline ..... C 10 H 8 212 Paranaphthaline (anthracene) C 14 H 10 C TT Pyren ....... ^64 ^15 4 ... Water |H} 100 Hydrosulphuric acid .... {H} S ... Hydrosulphocyanic acid |(CN)} S Carbonic oxide ..... CO Carbonic anhydride .... C0 2 . . . Bisulphide of carbon .... CS 2 47 Sulphurous anhydride .... SO 2 - 10 Acetic acid 1 (C 2 H 8 0) } I2O Carbolic acid (phenol) {(C 6 ^ 5 )} 188 Cresylic alcohol (cresol) i